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The oxygen evolution reaction (OER) underpins many aspects of energy storage and conversion in modern industry and technology, but which still be suffering from the dilemma of sluggish reaction kinetics and poor electrochemical performance. Different from the viewpoint of nanostructuring, this work focuses on an intriguing dynamic orbital hybridization approach to renormalize the disordering spin configuration in porous noble-metal-free metal-organic frameworks (MOFs) to accelerate the spin-dependent reaction kinetics in OER. Herein, we propose an extraordinary super-exchange interaction to reconfigure the domain direction of spin nets at porous MOFs through temporarily bonding with dynamic magnetic ions in electrolytes under alternating electromagnetic field stimulation, in which the spin renormalization from disordering low-spin state to high-spin state facilitates rapid water dissociation and optimal carrier migration, leading to a spin-dependent reaction pathway. Therefore, the spin-renormalized MOFs demonstrate a mass activity of 2,095.1 A gmetal-1 at an overpotential of 0.33 V, which is about 5.9 time of pristine ones. Our findings provide a insight into reconfiguring spin-related catalysts with ordering domain directions to accelerate the oxygen reaction kinetics.
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Li-CO2 battery provides a new strategy to simultaneously solve the problems of energy storage and greenhouse effect. However, the severe polarization of CO2 reduction and CO2 evolution reaction impede the practical application. Herein, anodic TiO2 nanotube arrays are first introduced as carbon-free and free-standing cathode for photo-assisted Li-CO2 battery, and the photo-assisted charge and discharge mechanism is first clarified from the perspective of photocatalysis. Mixed-phase TiO2 exhibits a long cycling life of 580 h (52 cycles) at 0.025 mA cm-2 and delivers a high discharge specific capacity of 3001 µAh cm-2 under UV illumination. The charge voltage dramatically reduces from 4.53 to 3.03 V under UV illumination. The improvement of photo-assisted Li-CO2 battery performance relies on the synergistic effect of the hierarchical porous structure, strong UV absorption, efficient separation, and transfer of photo-generated electrons and holes at hetero-phase junction, and the facilitation of photo-generated electrons and holes on CO2 reduction and CO2 evolution reaction. This work can provide useful guidance for designing efficient photocathode for photo-assisted Li-CO2 battery and other metal-air batteries.
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Perovskite materials are prominent candidates for many high-performance optoelectronic devices. The rare-earth lead-free CsEuCl3 perovskite nanocrystals are extremely unstable, which makes it very difficult to study their physicochemical properties and applications. Herein, we improved the stability of rare-earth based CsEuCl3 nanocrystals by employing a silica-coating for the first time. Simultaneously, the naturally formed "hollow" regions with an obviously blue-shifted PL emission were first observed inside the CsEuCl3 nanocrystals during the period of storage. Density functional theory (DFT) calculations showed that the formed "hollow" regions are due to the internal defect evolution in the perovskite lattice, which is also responsible for the increase of the bandgap and the blue-shift of emission. Additionally, the rapid decline of luminescence is probably due to the nanocrystals' final cracking with the expansion of the "hollow" regions. This work helps to understand the relationship between defects and luminescence properties, and provides guidance for the design of more stable lead-free perovskite nanocrystals.
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Correction for 'Enhanced photoluminescence stability and internal defect evolution of the all-inorganic lead-free CsEuCl3 perovskite nanocrystals' by Yalei Gao et al., Phys. Chem. Chem. Phys., 2022, 24, 18860-18867, https://doi.org/10.1039/D2CP01374F.
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Highly efficient H2 production from water splitting has been achieved by N-doped titanate nanotubes (N-TNTs) decorated with graphene quantum dots (GQDs) in this work. In order to promote charge carrier transmission at the interface, a facile and environmentally friendly in situ growth method was employed to construct a strongly coupled N-TNT/GQD composite photocatalyst. The results revealed that N atoms were effectively doped into the crystal lattice of the TNTs in the form of both interstitial N and substitutional N, and the GQDs were decorated onto both the inner and outer surfaces of the N-TNTs through the formation of Ti-O-C chemical bonds. Photoelectrochemical measurements proved that, in N-TNT/GQD composite, N-doping can extend light response to the visible-light range, and the coupling with GQDs not only enhanced visible-light absorption, but also promoted interfacial charge carrier transfer. Due to the synergistic effect between N-doping and GQD coupling, the closely integrated N-TNT/GQD composite exhibits a much superior photocatalytic H2 production performance under UV-vis irradiation, being 2.1 times higher than that of pure TNTs.
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Non-volatile photomemory based on photomodulated luminescent materials offers unique advantages over voltage-driven memory, including low residual crosstalk and high storage speed. However, conventional materials have thus far been volatile and insecure for data storage because of low trap depth and single-level storage channels. Therefore, the development of a novel non-volatile multilevel storage medium for data encryption remains a challenge. Herein, a robust, non-volatile, multilevel optical storage medium is reported, based on a photomodulated Ba3MgSi2O8:Eu3+, which combined the merits of light-induced valence (Eu3+ â Eu2+) and photochromic phenomena using optical stimulation effects, accompanied by larger luminescent and color contrasts (>90%). These two unique features provided dual-level storage channels in a single host, significantly improving the data storage security. Notably, dual-level optical signals could be written and erased simultaneously by alternating 265 and 365 nm light stimuli. Theoretical calculations indicated that robust color centers induced by intrinsic interstitial Mg and vacancy defects with suitable trap depths enable excellent reversibility and long-term storage capability. By relying on different luminescent readout mechanisms, the encrypted dual-level information can be accurately decrypted by separately probing the Eu2+ and Eu3+ signals, thus ensuring information security. This study proposes a novel approach for constructing multilevel information storage channels for information security.
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Dense and flat La[Formula: see text]NiFeO[Formula: see text] (LNFO) films were fabricated on the indium tin oxide-coated glass (ITO/glass) substrate by sol-gel method. The bipolar resistive switching behavior (BRS) could be maintained in 100 cycles and remained after 30 days, indicating that the LNFO-based RS device owned good memory stability. Surprisingly, the multilevel RS characteristics were firstly observed in the Au/LNFO/ITO/glass device. The high resistance states (HRSs) and low resistance state (LRS) with the maximum ratio of [Formula: see text] 500 could be remained stably in 900 s and 130 cycles, demonstrating the fine retention and endurance ability of this LNFO-based RS device. The BRS behavior of Au/LNFO/ITO/glass devices primarily obeyed the SCLC mechanism controlled by oxygen vacancies (OVs) dispersed in the LNFO layer. Under the external electric field, injected electrons were captured or discharged by OVs during trapping or detrapping process in the LNFO layer. Thus, the resistive state switched between HRS and LRS reversibly. Moreover, the modulation of Schottky-like barrier formed at the Au/LNFO interface was contributed to the resistive states switchover. It was related to the change in OVs located at the dissipative region near the Au/LNFO interface. The multilevel RS ability of LNFO-based devices in this work provides an opportunity for researching deeply on the high density RS memory in lead-free double perovskite oxides-based devices.
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A method for gram-scale synthesis of graphitic carbon nitride quantum dots (g-C3N4QDs) was developed. The weight of the g-C3N4QDs was up to 1.32 g in each run with a yield of 66 wt%, and the purity was 99.96 wt%. The results showed that g-C3N4QDs exhibit a stable and strong ultraviolet photoluminescence at a wavelength of 365 nm. More interestingly, the g-C3N4QDs can be used as a high-efficiency, sensitive, and selective fluorescent probe to detect Fe3+ with a detection limit of 0.259 µM.
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Light-modulated lead-free perovskites-based memristors, combining photoresponse and memory, are promising as multifunctional devices. In this work, lead-free double perovskite Cs2AgBiBr6 films with dense surfaces and uniform grains were prepared by the low-temperature sol-gel method on indium tin oxide (ITO) substrates. A memory device based on a lead-free double perovskite Cs2AgBiBr6 film, Pt/Cs2AgBiBr6/ITO/glass, presents obvious bipolar resistive switching behavior. The ROFF/RON ratio under 445 nm wavelength light illumination is ~100 times greater than that in darkness. A long retention capability (>2400 s) and cycle-to-cycle consistency (>500 times) were observed in this device under light illumination. The resistive switching behavior is primarily attributed to the trap-controlled space-charge-limited current mechanism caused by bromine vacancies in the Cs2AgBiBr6 medium layer. Light modulates resistive states by regulating the condition of photo-generated carriers and changing the Schottky-like barrier of the Pt/Cs2AgBiBr6 interface under bias voltage sweeping.
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High-quality CH3NH3PbI 3-xClx (MAPIC) films were prepared using potassium chloride (KCl) as an additive on indium tin oxide (ITO)-coated glass substrates using a simple one-step and low-temperature solution reaction. The Au/KCl-MAPIC/ITO/glass devices exhibited obvious multilevel resistive switching behavior, moderate endurance, and good retention performance. Electrical conduction analysis indicated that the resistive switching behavior of the KCl-doped MAPIC films was primarily attributed to the trap-controlled space-charge-limited current conduction that was caused by the iodine vacancies in the films. Moreover, the modulations of the barrier in the Au/KCl-MAPIC interface under bias voltages were thought to be responsible for the resistive switching in the carrier injection trapping/detrapping process.
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To research and develop potential multifunctional nanoprobes for biological application, lanthanide-doped MCM-41 (Ln-MCM-41, Ln = Gd/Eu) silica nanoparticles with excellent pore structure and optical-magnetic properties were synthesized via a facile and economical sol-gel method. The microstructure and pore distribution of Ln-MCM-41 nanoparticles were obviously affected by the Ln-doping. As the Ln/Si mole ratio increased, the specific surface area and total pore volume of Ln-MCM-41 nanoparticles rapidly decreased. However, the Ln-MCM-41 nanoparticles still retained the typical well-ordered mesoporous structure, and exhibited excellent drug release behavior. Moreover, the drug release rate of Ln-MCM-41 was remarkably pH-dependent and increased gradually upon decreasing pH. Additionally, these nanoparticles also exhibit considerable photoluminescence properties, living cells photoluminescence imaging in vitro, and paramagnetism behavior at room temperature due to the Ln3+-ions doping. Our research shows the possibility of our Ln-MCM-41 nanoparticles as multifunctional nanoprobes for application in bioseparation, bioimaging, and drug delivery.
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Inducing magnetic moments in graphene is very important for its potential application in spintronics. Introducing sp³-defects on the graphene basal plane is deemed as the most promising approach to produce magnetic graphene. However, its universal validity has not been very well verified experimentally. By functionalization of approximately pure amino groups on graphene basal plane, a spin-generalization efficiency of ~1 μB/100 NH2 was obtained for the first time, thus providing substantial evidence for the validity of inducing magnetic moments by sp³-defects. As well, amino groups provide another potential sp³-type candidate to prepare magnetic graphene.
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Nitrogen-doped graphene quantum dots (NGQDs) were synthesized by irradiating graphene quantum dots (GQDs) in an NH3 atmosphere. The photoluminescence (PL) properties of the GQDs and the NGQDs samples were investigated. Compared with GQDs, a clear PL blue-shift of NGQDs could be achieved by regulating the irradiating time. The NGQDs obtained by irradiation of GQDs for 70 min had a high N content of 15.34 at % and a PL blue-shift of about 47 nm. This may be due to the fact that photochemical doping of GQDs with nitrogen can significantly enhance the contents of pyridine-like nitrogen, and also effectively decrease the contents of oxygen functional groups of NGQDs, thus leading to the observed obvious PL blue-shift.
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Doping of low-dimensional graphitic materials, including graphene, graphene quantum dots and single-wall carbon nanotubes with nitrogen, sulfur or boron can significantly change their properties. We report that simple fluorination followed by annealing in a dopant source can superdope low-dimensional graphitic materials with a high level of N, S or B. The superdoping results in the following doping levels: (i) for graphene, 29.82, 17.55 and 10.79 at% for N-, S- and B-doping, respectively; (ii) for graphene quantum dots, 36.38 at% for N-doping; and (iii) for single-wall carbon nanotubes, 7.79 and 10.66 at% for N- and S-doping, respectively. As an example, the N-superdoping of graphene can greatly increase the capacitive energy storage, increase the efficiency of the oxygen reduction reaction and induce ferromagnetism. Furthermore, by changing the degree of fluorination, the doping level can be tuned over a wide range, which is important for optimizing the performance of doped low-dimensional graphitic materials.
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Inducing robust magnetic moments on the basal plane of the graphene sheet is very difficult, and is one of the greatest challenges in the study of physical chemistry of graphene materials. Theoretical studies predicted that introduction of a kind of sp(3)-type defects formed by OH groups is an effective pathway to achieve this goal [Boukhvalov, D. W. &Katsnelson, M. I. ACS Nano 5, 2440-2446 (2011)]. Here we demonstrate that OH groups can efficiently induce robust magnetic moments on the basal plane of the graphene sheet. We show that the inducing efficiency can reach as high as 217 µB per 1000 OH groups. More interestingly, the magnetic moments are robust and can survive even at 900°C. Our findings highlight the importance of OH group as an effective sp(3)-type candidate for inducing robust magnetic moments on the basal plane of the graphene sheet.
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The long spin diffusion length makes graphene very attractive for novel spintronic devices, and thus has triggered a quest for integrating the charge and spin degrees of freedom. However, ideal graphene is intrinsic non-magnetic, due to a delocalized π bonding network. Therefore, synthesis of ferromagnetic graphene or its derivatives with high magnetization is urgent due to both fundamental and technological importance. Here we report that N-doping can be an effective route to obtain a very high magnetization of ca. 1.66 emu/g, and can make graphene oxide (GO) to be ferromagnetism with a Curie-temperature of 100.2 K. Clearly, our findings can offer the easy realization of ferromagnetic GO with high magnetization, therefore, push the way for potential applications in spintronic devices.
Asunto(s)
Grafito/química , Campos Magnéticos , Imanes , Nitrógeno/química , Óxidos/química , Diseño de Equipo , Análisis de Falla de Equipo , Ensayo de MaterialesRESUMEN
Fluorination was confirmed to be the most effective route to introduce localized spins in graphene. However, adatoms clustering in perfect graphene lead to a low efficiency. In this study, we report experimental evidence of the generation of localized spin magnetic moments on defective graphene (reduced graphene oxide) through fluorination. More interstingly, the result shows that defects help increase the efficiency of the fluorination with regard to the density of magnetic moments created. Fluorinated reduced graphene oxide can have a high magnetic moment of 3.187 × 10(-3) µB per carbon atom and a high efficiency of 8.68 × 10(-3) µB per F atom. It may be attributed to the many vacancies, which hinder the clustering of F atoms, and introduce many magnetic edge adatoms.